Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
  • B29C64/10—Processes of additive manufacturing
  • B29C64/165—Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
  • B29C64/30—Auxiliary operations or equipment
  • B29C64/35—Cleaning
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
  • B29C64/30—Auxiliary operations or equipment
  • B29C64/386—Data acquisition or data processing for additive manufacturing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y10/00—Processes of additive manufacturing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
  • B33Y40/20—Post-treatment, e.g. curing, coating or polishing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y50/00—Data acquisition or data processing for additive manufacturing
  • B33Y50/02—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y70/00—Materials specially adapted for additive manufacturing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y80/00—Products made by additive manufacturing
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica

Definitions

• Methods of fabricating three-dimensional (“3D”) polymeric parts may include Hght area printing LAP”) s selective laser sintering ("SLS"), Inkjet binder sintering, fused deposition modeling rFDM “ ), stereoiithography f SLA * ), and digital light projection (“DIP”) sintering.
• Final 3D parts produced from these methods often experience a reduction in physical dimensions of at least 5% (before compensation) during the fabrication process.
• the reductio is often due to the tow density of the layers, which density generally ranges from 20 to 50%, and the rest of the layer volume is taken up either b a binder or the air voids,
• FIG. 1 provide a schematic flowchart illustrating one example of a 3D printing process described herein.
• FIG. 2 provide a schematic flowchart illustrating another example of a 3D printing process described herein.
• FIGS. 3A-3E provide schematic diagrams illustrating cross-sectional views of the processes involved in one example of forming object slices of a 3D object using an example of a 3D printing method described herein.
• FIG. 4 is a simplified Isometric view of an example of a 3D printing system that may b used I one example of the 3D printing method as disclosed herein.
• FIG. 5 provides a flowchart describing processes involved in one example of an LAP method described herein.
• FIG. 6 provides a schematic illustrating, in one example, the cross-section of an object slice comprising micrometer-sized polymeric partscies and a plurality of nanoparticles located between the polymeric particles.
• a three-dimensional (“3D" ⁇ printing method comprising: (A) forming a layer compnsing (i) particles comprising a polymer and (ii) cavities between the partscies, wherein the particles have an average diameter of between about 5 pm and about 260 pm; (8) disposing a liquid suspension over at least a portion of the layer such that the liquid suspension infiltrates into the cavities, wherein the liquid suspension comprises a radiation-absorbing coalescent agent and nanoparticles having an average diameter of less than or equal to about 500 nm; (C) forming an object slice of a 3D object by exposing the infiltrated layer to a radiant energy, wherein the object slice comprises a polymeric matrix comprising the polymeric particles, at least some of which are fused to one another, and the nanoparticles within the polymeric matrix; and (D) repeating (A) to (C) to form the 3D object comprising multiple object slices bound depth-wise to one another,
• a three-dimensional f3D printing method, comprising: (A) forming a layer comprising (i) mono-dispersed particles comprising a thermoplastic and (ii) cavities between the particles, wherein the particles have an average diameter of between about 10 pm and about 150 pm; (8) disposing an aqueous liquid suspension over at least a portion the layer such that the liquid suspension infiltrates into the cavities, wherein the liquid 84030581
• suspension comprises a radiation-absorbing coaSescent agent and nanoparticles having an average diameter of between about SO nm and about 500 nm; (C) exposing the infiltrated layer to a radiant energy, such thai the coalescent agent absorbs the energy and fuses at least some of the particies in the infiltrated layer; (D) solidifying the exposed layer to form an object slice of a 3D object, wherein the object slice comprises a polymeric matrix comprising the fused particies and the nanoparticles within the polymeric matrix, and wherein the object slice is at least substantially free of the cavities; and (E) repeating (A) to (C) to form the 3D object comprising multiple object slices bound depth-wise to one another,
• a three-dimensional (“3D" ⁇ printing system comprising: a first device to form a layer; a second device to dispose a liquid suspension; an energy source to apply a radiant energy; and a controller to execute instructions to: cause the first device to form the layer comprising (i) particles comprising a poiymer and (is) cavities between the particles, wherein the pariicles have an average diameter of between about S ptn and about 250 pm; cause the second device to dispose over at least a portion of the layer the liquid suspension such that the liquid suspension infiltrates into the cavities, wherein the liquid suspension comprises a radiation-absorbing coalescent agent and nanoparticles having an average diameter of less than or equal to about 500 nm; and cause the energy source to apply the radiant energy to the infiltrated layer to form an object slice of a 3D object, wherein the object slice comprises a
• polymeric matrix comprising the particies, some of which are fusee! to one another, and the nanoparticles within the polymeric matrix.
• Polymeric Particles 00131 The particies comprising the poiymer in the aforementioned layer described herein may comprise any suitable material. These polymeric particles (or “particles” for short herein) may comprise mono-dispersed particles of the same size.
• size herein may refer to length, width, height, diameter, etc Also, 84030581
• any of the dimensions described herein may refer to a statistical average.
• the term "mono-dispersed” may refer to above at least 80% of the particles having the same size - e.g., at least about 85%, about 90%, about 95%, about 99%, about 99,5%, or higher.
• These particles may have the same chemical composition, or the may have multiple types of chemical compositions.
• the particles may comprise any suitable polymeric material.
• the particles may comprise a thermoplastic.
• suitable polymers for the particles include polyamide, polystyrene, polyethylene, polyacetal, polypropylene, polycarbonate, polyurethane, and blends of any two or more of the aforementioned an&or other polymers.
• the weight-average molecular weight of the polymer employed in the particles may range from about 25,000 to about 350,000, Other molecular weight values are also possible, depending on the polymer involved.
• the polymer comprises a polyamide having weight-average molecula weight ranging from about 70,000 to about 300,000.
• the polymer may comprise, or be, a nylon, such as a high molecular weight nylon - e.g., polyamide ⁇ ") 12, polyamide 6, polyamide 8, polyamide 11, polyamide 88, and combinations thereof.
• the polydispersity i.e., the ratio of weight-average molecular weight to number-average molecular weight
• the polydispersity may range from 1 to 4,
• the particles may have a core-shell configuration.
• a core-shell polymer may include an internal polymer particle (i.e.. the core) that has a coating or layer (i .e., the shell) disposed thereon,
• the core and shell of a single particle may comprise different polymers (which have similar or different molecular weights), or may comprise the same type of polymer with different molecular weights.
• the core comprises a polymer having a high weight-average molecular weight ranging from 70,000 to about 300,000
• the shell comprises a polymer having a low weight-average molecular weight ranging from about 25,000 to less 84030581
• suitable core polymers include nylons, such as high molecular weight nylons - e.g., poiyamide 12. poiyamide 8, poiyamide 8, poiyamide 11 , poiyamide 66, and combinations thereof.
• suitable shell polymer include low molecular weight nylons such as poiyamide 12.
• poiyamide 12 is se lected for both the core and l e shell, it is to be understood thai the weight-average molecular weight of tt e core ranges from about 70,000 to about 300,000. and the weight-average molecular weight of the shell ranges from about 25,000 to less than about 100,000, In another example, any of the low weight-average molecular weight polymers is selected as the core, and any of the high weight-average moiecuSar weight polymers is selected as the shell.
• core-shell particles with different polymer type cores and shells include a shell of poiyamide, and a core selected from poiyether ketones, polycarbonates, acryionitrsle butadiene styrene (ASS) polymers, poiyurethanes, and acrylic polymers.
• a shell of poiyamide and a core selected from poiyether ketones, polycarbonates, acryionitrsle butadiene styrene (ASS) polymers, poiyurethanes, and acrylic polymers.
• the polymeric particles may have any suitable geometry, including size and shape.
• the particies may be spherical, ellipsoidal, cubical, cylindrical, spiny, wire-like, sheet-like, flake-like, etc.
• the polymeric particles may have an irregular geometry, in one example, the polymeric particles described herein are spherical.
• the term "spherical” herein may encompass a shape that is a perfect sphere or almost spherical
• the term "almost spherical” may refer to a shape that resembles a sphere but is not completely spherical, such as having a relatively small amount of irregularity deviating from a perfect spherical shape.
• a spherical particle herein ma refer to a particle having a sphericity of at least about 0.80 - e.g., at least about 0.85, about 0.90, about 0,95, or higher.
• the particies in the pulverulent layer may have any suitable size.
• the particles may have an average diamete in the micrometer range.
• the particies may have an average diameter of at least about 1 pm ⁇ e.g., at least about 5 pm, about 1 pm, about 50 pm, about 100 pm, about 150 pm, about 200 pm, about 250 pm, about 300 pm, about 400 pm. about 500 pm, or 84030581
• the particles have an averag diameter of between about 1 pm and about 500 pm, between about 2 pm and about 400 pm, between about 5 pm and about 250 pm, between about 10 pm and about 200 pm, between about 20 pm and about 100 pro, etc.
• the particles may be mono- dispersed (with respect to size) and/or have the same chemical composition, or the particles may have multiple sizes (and/or size distributions ⁇ and/or chemical compositions.
• fOGISJ The particles may foe physically modified, so that the surface topography of the particles is altered. Physical modifications ma be accomplished using a milling process, a precipitation process, and/or a spraying deposition process.
• the surface topography of the particles is modified so that nodules are present at the respective surfaces of the particles after the modification process is complete.
• Nodules are small profusions features that extend outward from the surface of a particle.
• Each nodule may have a diameter or a average diameter ranging from about 50 nm to about 5 pm.
• nodules present at the surfaces of the particles may increase the contact surface area of the particles with neighboring particles in the layer (disposed over a substrate) comprising the polymeric particles.
• the nodules may increase the efficiency of any sintering, fusing, curing process that is subsequently performed involving the particles,
• the particles may be chemically modified, such as at the surface thereof. Chemical surface modifications may be performed to improve the wetting of the polymeric particles with subsequently deposited materials (i.e., to facilitate improved fluid interaction), and/or to enhance cross-linking between the particles during sintering, fusing, curing, etc. thereby enhancing the mechanical strength and elongation performance of the resultant 3D object.
• the wetting angle of the polymeric particles may be modified to be less than 45°. This wetting angle may increase the ability of subsequently deposited 84030581
• a wetting angle of less than 45 c may be achieved by introducing chemical building blocks, such as hydroxy! groups, onto the surface of the particles.
• hydroxy! groups Is introduced onto the surface of the particles by treating the particles with hydroxyi-oonfaining compounds, such as glycerol, pentanedio!, hexanediol, and pentaerythritol.
• the polymeric particles include carboxylic acid and/or amino functional groups at the surface
• chemical modification may take place through these functional groups
• the polymeric particles including the carboxylic acid and/or amino functional groups at the surface may be treated with an amino compound having the genera! structure RNH s XR", where R is H or an aikyl group with 1 to 18 carbon atoms; R : is a divalent linking group (such as an alkylene or aryiene); XR" together is H, or X is selected from O, COO, OCO,
• R " is selected from H or an aikyl group with 1 to 18 carbon atoms.
• the corresponding salt(s) or amido group(s) may be formed on the surface of the particles. Not to be baun0 by any particular theory, but the addition of the salt(s) or amido group(s) at the surface of the particles ma improve inferlayer adhesion, enable better flow when the particles melt and/or adjust the hydrophobiciiy of the 3D object that is formed,
• the polymeric particles including the carboxylic acid and/or amino functional groups at the surface may be treated with an alcohol having the general structure of HOR'XR * .
• R' is a divalent linking group ⁇ e.g., an alkylene or aryiene
• XR * together is H, or X is selected from O, COO, OCO, CO H : NHCO, or CO and R" is selected from H or an aikyl group with 1 to 18 carbon atoms.
• an ester group may b formed on th surface of the particles.
• the addition of the ester group(s) at the surface of th particles may also improve inter!ayer adhesion, enable better flow when the particles melt and/or adjust the hydrophofoicity of the 3D object that is formed.
• the polymeric particles including the amino functional groups at the surface are treated with chioro or alkoxy silanes.
• a suitable silane Is YSi(P3 ⁇ 4 ⁇ T, where Y Is CI, OCH 3 , or OCH2CH 3 ; is an alky! or alkoxy group with 1 to 18 carbon atoms; and R" is an aikyl group with 1 to 18 carbon atoms or an aikyl group with substifuent groups having 1 to 18 carbon atoms.
• the addition of the silane group(s) at the surface of the particles may improve interiayer adhesion, enable better flow when the particles melt, and/or adjust the hyd ophobicity of the 3D object that is formed,
• the particles may be present in the form of a powder, a liquid, a paste, or a gel.
• Examples of the polymer in the particles include semi-crystalline
• thermoplastics with a processing window of greater tha 5 a C - i.e., the
• the processing window ranges from 15 C to about 3G ⁇ l C.
• the polymer include polyamldes ⁇ e.g., nylon or PA 11 f PA-H"), nylon or PA 12 ( ⁇ -12 * ), nylon or FA 8 (VM * nylon o PA 8 fPA-8 8 ⁇ , nylon or PA 9 fPA-9 s , nylon or PA 6 ⁇ f PA-66 * ), nylon or PA 61 CPA ⁇ 612 S ), nylon o PA 812 ( * ⁇ -812 3 ⁇ 4 ), nylon or PA 912 fPA-912 s ), etc.
• Other examples of the polymer include polyethylene, polyethylene terephthalate (PET), and
• the polymer in the particles may have a melting temperature of any suitable value, depending on the materia! Involved.
• the melting temperature may range from about 50 to about 400 .
• po!yamide 12 having a melting temperature of about 180 e C may be employed, or
• polyurethanes having a melting temperature ranging from about 100 ft C to about 185 °C may be employed.
• at least one of lie particles has a melting temperature below the melting temperature of the inorganic salt in the modifier agent.
• each of the plurality of polymeric particles has a melting temperature below the melting temperature of the inorganic salt
• the layer comprising the polymeric particles may additionally comprise a charging agent, a flow aid. or combinations thereof.
• a charging agent may he added to suppress thbo-eharging.
• suitable charging agent include aliphatic amines (which may be ethoxylated), aliphatic amides, quaternary ammonium salts (e.g., behentrimonium chloride or cocamidopropyi
• the charging agent is added in an amount ranging: from greater than 0 wt% to less than 5 wt% based upon the total wt% of the particles. Other amount of the charge agent is also possible.
• Flow aid(s) may he added to improve the coating flovvabllity of the polymeric particles.
• Flow aid(s may be desirable when the particles have an average diameter of less than about 26 pm in size.
• the flow aid may improve the fiowabsility of the polymeric particles by reducing the friction, the lateral drag, and the thbocharge buildup (by increasing the particle conductivity).
• suitable flow aids include trica!cium phosphate (E341), powdered cellulose
• the flow aid is added in an amount ranging from greater than 0 wt% to less tha S wt% based upon the total wt% of the particles.
• the coaiescent fluid described herein to facilitate forming a 3D object may comprise a liquid suspension.
• the liquid suspension may contain an suitable number of components.
• the liquid suspension of t e coaiescent fluid may contain a coaiescent agent.
• the coaiescent agent may be energy-absorbing, such as radiation-absorbsng. The energy may refe to radiant energy.
• Examples of tie suitable liquid suspension described herei include an aqueous dispersion containing at least one coaiescent agent.
• the radiation-absorbing agent may bo an Infrared light absorber, a near infrared light absorber, or a visible light absorber.
• Absorption tierein may refer to attenuation of the energy of a beam (light, electrons, etc, ⁇ on passage through a matter. The dissipated energy as a result in this instance may be converted into other forms of energy (e.g. , heat).
• An absorber may refer to a piece of matter, or body, intended to absorb radiation. An absorber herein may absorb all of, or a major proportion of, radiation i the region from 100 nm to 1 mm. The radiation may be non-monochromatic and/or non-coherent and/or non-oriented, of wavelength from 100 nm to 1 mm, such as via a radiative heater or any other energy source described in this disclosure herein.
• a coaiescen agent acts as an absorber to absorb t e energy and dissipate it in the form of heat to its surrounding particles in the pulverulent layer.
• a coaiescen agent acts as an absorber to absorb t e energy and dissipate it in the form of heat to its surrounding particles in the pulverulent layer.
• Such a process may allow a large number of materials to be used than a sin ehng-hased ⁇ e.g., laser sintering) process, in one example, the polymeric particles in the pulverulent layer generally are incapable, or insufficiently 84030581
• insufficiently in ibis context refers to that absorption of radiation via an energy source of a wavelength from 100 nm to 1 mm does not heat the pulverulent layers sufficiently to enable it to bond via fusion or sintering to adjacent pulverulent layer particles, or thai the time needed for this is impractieaSly long.
• the absorption herein may refer to a subset of the 100 nm to 1 mm range ⁇ e,g, s between about 700 nm and about 1400 nm.
• the coalescent agent may be a pigment-based: or a dye-based ink, in one example, the ink may comprise visible light enhancers) as the active agent.
• the coaieseent agent is an ink-type formulation including carbon black, such as, for example, the ink formulation commercially known as C 997A available from Hewlett-Packard Company, Examples of inks including visible light enhancers are dye-based colored inks and pigment-based colored inks, such as the commercially available inks CE039A and CEG42A, available from Hewlett- Packard Company, Not to be bound by any particula theory, but the aqueous nature of some coaieseent agent may enabl the coalescent agent to penetrate and infiltrate the base layer comprising polymeric particles.
• coalescent agent For hydrophobic polymeric particles the presence of a co-solvent and/or a surfactant in the coalescent agent may assist in obtaining the desired wetting.
• One or more coalescent agent may be dispensed to form each object slice (of the final resultant 3D object),
• the coalescent agent may comprise water soluble near-inf ared absorbing dyes with absorptions in the range of about 800 nm to about 1400 nm as the main component in the coalescent agent.
• the fusing lamp in an LAP process emits radiation energ (e.g., light) ove the about 800 nm to about 1400 nm range.
• using a near-I fNIR * ) absorbing dye as the coalescent agent (or a part thereof) may overcome a challenge of creating a resultant product that is black or grey in color and has poor visual uniformity (or optical density), sometimes as a result of using carbon black.
• the dye may achieve the desired fusing efficiency and improve the color uniformity.
• the maximum emissive light occurs around 100 nm and quickly forms a tail end.
• the dyes employed should have similar absorption range for maximum efficiency.
• coiored parts with a wide spectrum of color gamut ma he obtained with incorporation of colored pigments and dyes.
• solvent soluble dyes in the absorption range of about 800 nm to about 1400 nm are dispersed with surfactants.
• the thermal properties of the base polymeric particle pulverulent layer may impact the quality (e.g., mechanical properties) of the resultant 3D object
• water soluble dyes or compounds that have absorptions in the about 800 nm to about 1400 nm range are employed as to increase, or even maximize, the absorption of fusing emissive lamp. These dye may be washed off at the end so that the surface of the part does not contain any residual dyes.
• the coalescent agent is an organic near-infrared dyes, which are stable in the ink formulation.
• T e MIR dyes may be any of the suitable commercially available S dyes and maintain their solubility in th presence of co-solvent in the designated ink vehicles.
• experiments with nylon and thermoplastic poiyureihane ⁇ powder particles using the NIR dyes as a coalescent agent show these dyes as strong heat generators upon exposure to a fusing lamp, similar to the process with carbon black based Ink as a coalescent agent.
• the amount of coalescent needed to achieve good powder fusing may be of any suitable value, depending on the material involved.
• the amount is in the range of about 0,5 wt% to about 8 wt% with respect to the powdersTM e.g. : about 1 wt% to about 6 wt% ( about 2 wt% to about 4 wt%, etc.
• Other values are also possible.
• with a concentration of less than about 2.5 wt% the final object obtained resembles closely the nature white color of nylon or TPU powders, in one example, these dyes are formulated into water- 84030581
• Inkjet ink dispersions show reasonably good jetting performance.
• various colored organic and/or inorganic pigments are added to the Ink/coaSeseent fluid dispersions so that f ey may be introduced during the iayer-by -layer fabrication process
• primary color inkjef ink pens may be used for generating colored objects in addition to the pen with near infrared dyes.
• the coalescent agent may contain carbon black (pigment).
• the carbon black pigment may act as a radiation absorbing agent or active material.
• Examples of carbon black pigments include those manufactured by Mitsubishi Chemical Corporation, Japan (such as, e.g., carbon black No. 2300, No. 900, CF88, No. 33, No. 40, No. 45, No. 52, A7, MAS, MA100, and No.
• RAVEN* series manufactured by Columbian Chemicals Company, Marietta, Georgia, (such as, e.g., AVEN** 5750, RAVEN * 5250, RAVEN ® 5000, RAVEN ® 3500, RAVEN ® 1255, and RAVEN* 700); various carbon black pigments of the REGAL ® series, the MOGUL ® series, or the MONARCH * series manufactured by Cabot Corporation, Boston, Massachusetts, (such as, e.g.
• the carbon black pigment may e polymericaiiy dispersed in the
• the carbon black pigment is initially in the form of a water-based pigment dispersion.
• the water-based pigment dispersion includes the carbon black pigment (which is not surface treated), the polymeric dispersani, and water (with or without a co-solvent).
• an example of the co-solvent may 84030581
• the polymeric dispersant may be any styrene acryiate or any polyuretbane having its weight average molecular weight ranging from about 12,000 to about 20,000, Some commercially available examples of the styrene acryiate polymeric dispersant are JONCRYL ⁇ 871 and JONCRYL ⁇ 683 (both available from: BASF Corp.).
• a ratio of the carbon black pigment to the polymeric dispersant ranges from about 3.0 to about 4,0, In an example, the ratio of the carbon black pigment to the polymeric dispersant is about 3.8. it is believed that the polymeric dispersant contributes to the carbon bisck pigment exhibiting enhanced electromagnetic radiation absorption.
• amount of the carbon black pigment that is present in the coalescent agent may range from about 3.0 wt% to about 8.0 wt% based on the total wt% of the coalescent agent, in other examples, the amount of the carbon black pigment present in tbe coalescent agent ranges from greater than 4.0 wt% op to about 6.0 wt%. Not to be bound by any particular theory, but these pigment loading levels may provide a balance between the coalescent agent having jetting reliability and electromagnetic radiation absorbance efficiency.
• the amount of the water-based pigment dispersion that is added to the coalescent agent may be selected so that the amount of the carbon black pigment in the coalescent agent is within the given ranges.
• the coalescent agent may compose an anti-kogation agent
• Kogatlon refers to the deposit of a dried ink (e.g., coalescent agent) on a beating element of a thermal InkJet prinihead.
• Antl-kogation agent(s) may be included to assist in preventing the buildyp of kogatlon.
• suitable anti-kogation agents include Qleth-3 ⁇ phospbate (e.g. : commercially available as CRQDAFOS G3A or C ODA OS® N-3 acid from Croda), or a combination of oleth ⁇ 3 ⁇ phos hate and a low molecular weight (e.g dislike ⁇ 6,000) polyacrylic acid polymer (e.g. , commercially available as CARBOSPERSE* K ⁇ ?028 Po!yacryiate from Lubrizol).
• a 84030581 e.g. : commercially available as CRQDAFOS G3A or C ODA OS®
• the total amount of ants-kogation agent(s ⁇ in the coalescent agent may range from greater than 0.20 wt% to about 0.82 wt% based on the total w ⁇ % of the coalescent agent, in an example, the o!eth-3-p osp ate is Included In an amount ranging from about 0.20 wt% to about 0,80 wt%, and the low molecular weight poiyscrylic acid polymer is included In an amount ranging from about 0.005 wt% to about 0.015 wt%,
• the coalescent agent may also include a chelator, a biocide/anti- microbial, and/or combinations thereof.
• the chelator may be added in any amount ranging from about 0.03 wt% to about 0.10 wt% based on the total weight of the coalescent agent.
• An example of a suitable chelator includes TRILO 3 ⁇ 4i (an aminopoiycarboxyiate, available from BASF Corp.),
• the biocide or antimicrobial may be added in any amount ranging from about 0.30 wt% to about 040 wt% with respect to the total weight of the coalescent agent.
• biocides anti-microbials examples include PRQXEL ⁇ GXL (an aqueous solution of 1 « 2- benzisothsazolsn-3-one s available from Arch Chemicals, Inc.) and KOROE ⁇ MLK (a formaldehyde-tee microbldde from the Dow Chemical Co.).
• the liquid suspension of the coalescent fluid may contain nanoparticles.
• the nanopartlcles may have any suitable geometry, including shape and size.
• the nanoparticSes ma have the same shape as any of the aforedescribed shapes of the polymeric particles.
• the nanopartlcles may have a different shape from the polymeric particles, in one example, the nanoparticles are spherical.
• T e nanoparticles may have an average diameter in the nanometer range.
• the average diameter may be less than or equal to about 600 nm ⁇ e.g., less than or equal to about 600 nm, about 400, about 300 nm, about 200 nm, about 100 m, abo t 50 nm, about 20 nm, about 10 nm, or smaller.
• the nanoparticles have an average diameter of between about 10 nm and about 500 nmTM e.g., about 20 nm and about 400 nm, about 30 nm and about 300 84030581
• the nanoparticies have an average diameter of betwee about 60 nm and about 250 nm.
• the nanoparticies may be present In the liquid suspension at any suitable amount - I.e., at a loading level of any suitable value.
• the suitable amount I.e., at a loading level of any suitable value.
• nanoparticles may be between about 1 wt% and about 50 wt% of the liquid suspension ⁇ e.g., about 2 wl% and about 40 wt%, about 5 wt% and about 30 wt%, about 1 w % and about 200 wt%, etc. Other values are also possible. In one example, the nanoparticles are present at between about 5 wt% and about 25 wt%.
• nanoparticies may comprise any suitable material:.
• the nanoparticles may comprise the same material as that of the aforedescribed polymeric particles.
• the nanoparticles may comprise the same polymer as the polymeric particles.
• the nanoparticles may comprise a different material from that of the polymeric particles.
• the nanoparticles may comprise an inorganic material.
• the inorganic material may comprises a ceramic, including an oxide, a carbide, a nitride, an oxynitride, and the like.
• the inorganic material includes at least one of silica, alumina, iitanla, zinc oxide, tungsten carbide, and the like.
• the nanoparticles may comprise a metal, such as a transition metal, a noble metal, etc: or the nanoparticles may comprise a metal alloy.
• the liquid suspension may additionally comprise at least one coalescence modifier agent.
• suitable coalescence modifier agent may separata individual polymeric particles to prevent the particles from joining together and solidifying as part of an object slice.
• suitable coalescence modifier agent include colloidal, dye-based, and polymer-based inks, as well as solid particles that have an average size less than the average size of the polymeric particles descried herein.
• the molecular mass of the coalescence modifier agent and its surface tension may be 84030581
• a salt solution Is employed as a
• coalescence modifie agent !n another example, Inks commercially known as C 996A and CN673A available from Hewlett-Packard Company are employed as a coalescence modifier agent.
• Suitable coalescence modifier agents may act to modify the effects of a coalescent agent by preventing polymeric particles from reaching temperatures above Its melting temperature during heating.
• a fluid that exhibits a suitable cooling effect may be used as this type of coalescence modifier agent, for example, when polymeric particles is treated with a cooling fluid, energy applied to the polymeric particles may be absorbed, evaporating the fluid to help mitigate, minimize, or even prevent polymeric particles from reaching their melting
• a fluid with a high water content may be a suitable coalescence modifier agent.
• coalescence modifier agents may be used.
• An example of a coalescence modifier agent, which may increase the degree of coalescence may include, for example, a piast!azer
• Another example of a coalescence modifier agent, which may increase the degree of coalescence may include a surface tension modifier to increase the wettability of the polymeric particles,
• the modifier agent may act to mitigate, minimize, or even prevent thermal bleed, such as to improve the surface quality, of the object slice and/or the final resultant 30 object.
• the modifier agent may include an inorganic salt, a surfactant, a co-solvent, a humeetant, a bioeide, and water, in one example, the modifier agent consists of these components. It has been found that this particular combination of components may effectively reduce or prevent coalescence bleed, at least in part bec yse of the presence of the inorganic salt.
• an inorganic salt employed in the modifier agent has a relati ely high heat capacity. 84030581
• the modifier agent capable of absorbing the radiation (and its associated thermal energy) applied thereto, and also capable of retaining a bulk of the thermal energy therein. As such, very little, if any, of the thermal energy may be transferred from the modifier agent to the polymeric particles, 0047
• the aforementioned inorganic salt may have a Sower thermal conductivity and/or a higher melting temperature than the thermal conductivity and/or melting temperature of the polymeric particles, and, in some instances, of the active material in the coaiesceiit agent.
• the inorganic sail upon absorbing radiation and thermal energy, the inorganic sail does not melt and also does not transfer a sufficient amount of heat to the surrounding polymeric particles.
• the modifier agent effectively reduces curing/fusing of the poiymenc particles when polymeric particles are in contact with both the coalescent agent and the modifier agent, and prevent curing when the polymeric particles are In contact with the modifier agent alone.
• An inorganic salt in the modifie agent may he water soluble.
• suitable water soluble inorganic salt include sodium iodide, sodium chloride, sodium bromide, sodium hydroxide, sodium sulfate, sodium carbonate, sodium phosphate, potassium iodide, potassium chloride, potassium bromide, potassium hydroxide, potassium sulfate, potassium carbonate, potassium phosphate, magnesium iodide : magnesium chloride, magnesium bromide, magnesium phosphate, and combinations thereof.
• the inorganic salt ma be present in an amount ranging torn about 5,0 wi% to about 50 wt% with respect to a total weight of the modifier agent. Other values are also possible,
• the modifier agent may also include a surfactant.
• the type and amount of the surfactant may be selected so that a contact angle thereof with the polymeric particles is less than 45 :> .
• the components of the modifier agent may be mixed together, and then the amount of surfactant adjusted to achieve the desirable 84030581
• a suitable amount of surfactant to achieve the desired contact angle ranges from about 0,1 wt% to about 10 wt% with respect to the total weight of th modifier agent.
• suitable surfactants include tetraethyfene glycol ethylene glycol 1 (e.g., LIPONIC* ' EG-1 from Lipo Chemicals, Inc., NJ, USA), a self-em lsifiabie, nonionic wetting agent based on acetylenic diol chemistry (e.g., SURFYNOL* SEF from Air Products and Chemicals, inc.), a nonionic fluorosurfactant (e.g., CAPSTONE ⁇ fluorosurfactanfs from DuPont, previously known as ZONYL ⁇ FSO).
• tetraethyfene glycol ethylene glycol 1 e.g., LIPONIC* ' EG-1 from Lipo Chemicals, Inc., NJ, USA
• the surfactant is an ethoxy!ated low-foam wetting agent (e.g., SURFYNOL* 440 or SURFYNOL® CT- 11 from Air Products and Chemical Inc.) or an ethoxyfated wetting agent and molecular defdamer (e.g., SU FYNOl 3 ⁇ 4i 420 from Air Products and Chemical Inc.).
• an ethoxy!ated low-foam wetting agent e.g., SURFYNOL* 440 or SURFYNOL® CT- 11 from Air Products and Chemical Inc.
• an ethoxyfated wetting agent and molecular defdamer e.g., SU FYNOl 3 ⁇ 4i 420 from Air Products and Chemical Inc.
• HLB hydrophic-IJpophilic balance
• suitable surfactants with a hydrophic-IJpophilic balance (“HLB”) less than 10 include non-ionic wetting agents and molecular def amsrs (e.g., SURFYNOL* 104E from Air Products and Chemical inc.) or water-soluble, non-ionic surfactants (e.g., TERG!TQL* T N-6 from The Dow
• the e claimedseent includes a combination of the surfactant with the HLB less than 10 (e.g., the self-emulsfebSe surfactant based on acetyfenio diol chemistry) and a non-tonic fluorosurfactant (e.g., CAPSTONE 5 ' FS- 35 from DuPont).
• the surfactant may contribute at least in part to filling the cavities between the polymeric particles in the layer,
• the total amount of surfactants ⁇ in the coalescent agent may range from about 0.5 wt% to about 1.4 wt% based on the total wt% of the coalescent agent, and in some Instances, the coalescent fluid.
• the surfactant having the HLB less than 10 is included in an amount ranging from about 0.5 wt% to about 1 ,25 t%, and the fluorosurfactant Is included in a amount ranging from about 0.03 wt% to about 0.10 wt%.
• the modifier agent may include a co-solvent, a
• a co-solvent is present in an amount ranging from about 1.0 wt% to about 32 wt%, a bumectant in an amount ranging from about 0.1 wt% to about 15 t%, and a biocide in an amount ranging from about 0.01 wt% to about 5 wt%, each of which is with respect to the total weight of the modifier agent.
• Suitable co-solvents include 2- hydroxyethyi ⁇ 2 ⁇ pyrollidinone ( 2-pyroliidinone, 1 s 8 ⁇ hexanedioS. and combinations thereof.
• Suitable humectants include DHS-ri dro yethylJ-S, S-dimeihyShydantoin (e.g., DANTOCOL ® DHF from tonza, Inc.), propylene glycol, exyiene glycol, buty!ene glycol, glyceryl triacetate s vinyl alcohol, neoagarobiose, glycerol, sorbitol, xyiltol, maltitol, polydextrose, quilSaia, glycerin, 2 ⁇ methyl-1,3-pro:panediol i and combinations thereof.
• DHS-ri dro yethylJ-S S-dimeihyShydantoin
• DANTOCOL ® DHF from tonza, Inc.
• propylene glycol exyiene glycol
• buty!ene glycol buty!ene glycol
• the co-solvent may have a boiling temperature of less than or equal to about 300 : C In some examples, the co-solvent has a boiling temperature of less than or e ual to about 250 *C.
• Some examples of the single co-solvent include 2-pyrroiidinone, 1,5- entanediol, tnethy!ene glycol, tetrae hyiene glycol, 2 ⁇ ethyi-1 ,3 ⁇ pfopaned!o! ? 1,8-hexanedoi, and iripropylene glycol methyl ether.
• the coalesced agent may include one of the listed co-solvents alone, or two or more of the listed co-solvents in combination, and excludes other co- solvents.
• the co-solvent is 2-pyrrolidinone
• the co-solvent 2 ⁇ pyrroiidlnone alone is included
• the co-solvent is a combination of 2-pyrrolidinone and 1 ,5-pentanedioS, these solvents alone are included.
• Suitable biocides may include an aqueous solution of 1 ,2- benzisotbiazolin-3-one (e.g., PRQXEl ⁇ GXL frorn Arcb Chemicals, inc.), quaternary ammonium compounds (e,g dislike SARDAC* 2250 and 2280, BARQUAT* 50-658, and CARSOGUAT 2S0-T, ail from tonza Ltd, Corp.), and an aqueous solutio of methylisothiazolone (e.g., KGRDEK ® MIX from the Dow Chemical Co.),
• 1 ,2- benzisotbiazolin-3-one e.g., PRQXEl ⁇ GXL frorn Arcb Chemicals, inc.
• quaternary ammonium compounds e,g dislike SARDAC* 2250 and 2280, BARQUAT* 50-658, and CARSOGUAT 2S0-T, ail from tonza Ltd, Corp.
• the coalescent agent may include water (e.g., deionszed water), a co- so!vent having a boiling temperature less than 300 * C, a surfactant having an HLB 84030581
• the amount of water in the coalescent agent may vary depending upon the amounts of the other components, but the water makes up a balance of the coalescent agent (i.e., a total wi% of the coalescent agent Is 100).
• [OOS43 3D printing Is a printing process thai may be employed to fabricate (solid) 3D objects from a digital model.
• 3D printing may be employed in rapid product prototyping, mold generation, and mold master generation, 30 printing techniques are often considered additive manufacturing processes because they may involve the application/generation of successive layers of material An additive
• Materials used in 3D printing often need (e.g., fusing), which for some materials may e accomplished using heat- assisted extrusion or sintering, and for other materials may be accomplished using digital light projection technology.
• LAP 3D printing
• An LAP method may involve any suitable roc ss rs).
• LAP may have lower cost and ac ieve taster throughput with good accuracy and roughness, in comparison to a sintering technique.
• fOOSSJ In one example, LAP involves layer by layer deposition of polymeric particles ⁇ e.g., nylon and/or thermoplastic polyurethane TPlT), etc.) of any suitable si2e(s).
• these particles are preheated close to aboyt 150 °C, and then a coalescent agent (e.g., carbon black), along with nanoparticies, in a liquid suspension coalescent fluid Is selectively disposed over the region in a layer where the object is to be formed. Then the whole layer is exposed to high intensity fusing iamp(s) with emissive wavelength of between about 900 nm and about 1400 nm to be absorbed by the coalescent 84030581
• a coalescent agent e.g., carbon black
• the polymer powder particles may be melted or sintered by raising its temperature close to their melting temperature as a result of this transformation.
• the next pulverulent layer (of the polymeric particles) is layered on top of the underlying layer, and the process is repeated till the desired final 3D object is formed, in this example, the final object is either black or grey colored due to the presence of carbon black; but the color of the final object may be different if a different pigment dye is used.
• FIG. 1 illustrates one example of the processes in one LAP method
• a layer comprising (i) particles comprising a polymer and Cii) cavities between the particles is formed (S101).
• the particles may have an average diameter of between about 5 pro and about 250 pm.
• a liquid suspension is disposed over at teas! a portion of the layer such that the liquid suspension infiltrate into the cavities (S102).
• the liquid suspension may comprise a radiation-absorbing coaiescent agent and nanoparticles having; a average diameter of less than or equal to about 500 nm.
• An object slice of a 3D object may be formed by exposing the infiltrated layer to a radiant energy (S103).
• the object slice may comprise a polymeric matrix comprising the polymeric particles, at least some of which are fused to one another, and the nanoparticles withi the polymeric matrix.
• any combination of the processes SI 01 to Si 03 may be repeated to form the 3D object comprising multiple object slices hom depth-wise to one another,
• a printing system comprising various suitable devices. Including an energy source, and a controller to execute (machine-readable) instructions to cause these devices to perform the aforementioned processes is also provided.
• [0S58J ig. 2 illustrates anothe example of th processes in one LAP method.
• a layer comprising (i) mono-dispersed particles comprising a thermoplastic and (it) cavities betwee the particles is formed (S201),
• the particles may have an average diameter of between about 10 pm and about 160 pm.
• an aqueous liquid suspension is disposed over at ieast a portion the 84030581
• the liquid suspension may comprise a radiation-absorbing coaiescent agent and
• the infiltrated layer is exposed to a radiant energy, such that the coaiescent agent absorbs the energ and fuses at least some of the particles in the infiltrated layer (S.203). Thereafter, the exposed layer is solidified to form an object slice of a 3D object (S204),
• the object slice may comprise a polymeric matrix comprising the fused particles and the nanopaftlc!es within the polymeric matrix, and the object slice may be substantially free of the cavities.
• any combination of the processes S201 to S204 may be repeated to form the 3D object comprising multiple object slices ho n depth-wise to one another,
• a printing system comprising various suitable devices, including an energy source, and a controller to execute (machine-readable) instructions to cause these devices to perform the aforementioned processes is also provided.
• FIG. 3A-3E The sequence of sections presented in Figs, 3A-3E illustrate one example of manufacturing a three-dimensional object 44
• An example of the 3D printing method using an example of the polymeric particle composition 10 disclosed herein is shown in Figs. 3A through 3E
• the 3D printing method as shown in Figs. 3A-3E is an LAP method, in one example, during light area processing, an entire layer of the polymeric particle composition 10 is exposed to radiation, but only a selected region of the polymeric particle composition 10 is fused and hardened to become a layer of a 3D object. In another example, the entire region of the polymeric particle composition 10 is fused. In the example as shown In Figs.
• a coaiescent agent is selectively deposited in contact with the selected region of the polymeric particle composition 10.
• the coaiescent agent penetrates (partiali or fully) into the layer of the polymeric particle composition 10 and infiltrates the cavities present in betwee the particles in the polymeric particle compositio 10.
• the coaiescent agent is capable of absorbing radiation and converting the absorbed radiation to thermal energy, which in turn metis or sinters the particles 12, 14, 6 that are in 84030581
• the respective particles 12, 14, 16 of the polymeric particle composition 10 may be formed of the same type of polymer, or of different types of polymers, or some of the particles 12, 14 may be formed of the same type of polymer and the other particles 18 may be formed of a different type of polymer.
• the polymer may be any of those aforedescribed with respect to polymeric particles. It is noted that while particles 12, 14, arid 16 are depicted in Figs. 3A-3E as three different types (e.g., size, chemical compositions, etc.) for illustration purpose, the methods and the layers described herein need not have more than one type of particte.
• the polymeric particle composition 0 may comprise mono-dispersed particles - i.e. particles 12, 14, and 16 have the same size.
• the particles 12, 14, and 18 may also have the same material chemistry.
• a printing system 18 for forming the 3D object includes a supply bed 20 ⁇ including a supply of the polymeric particle composition 0). a delivery piston 22, a roller 24, a fabrication bed 26, and a fabrication piston 28.
• Each of these physical elements may be operativel connected to a central processing unit (not shown) of the printing system 18.
• the central process unit may comprise, or be, a controller.
• the central processing unit e.g., running machine readable instructions stored on a non-transitory, tangible machine readabl storag medium
• the machine herein may refer to a processor, such as a computer.
• the data for the selective delivery of the polymeric particle composition 10, the coalescent agent, etc. may he derived from a model of the 3D object to be formed.
• the delivery piston 22 and the fabrication piston 28 may be the same type of piston, but are programmed to move in opposite directions. In one example, when a first object slice (layer) of the 3D object is to be formed, the delivery piston
• the fabrication piston 22 may be programmed to push a predetermined amount of the polymeric particle composition 10 out of the opening in the supply bed 20, and the fabrication piston
• the 23 may be programmed to move in the opposite direction of the delivery piston 22 in order to increase the depth of the fabrication bed 26.
• the delivery piston 22 may advance enough so that when the roller 24 pushes the polymeric particle composition 10 into the fabrication bed 26, the depth of the fabrication bed 26 is sufficient so that a layer 30 of the polymeric particle composition 10 may be formed over the bed 28 (acting as a substrate), in one example, the layer 30 disposed over the bed 26 may comprise a mono-layer of the polymeric particle composition 10.
• the roller 24 is capable of spreading the polymeric particle composition 10 into the fabrication bed 26 to form the layer 30, which may be relatively uniform in thickness.
• the thickness of the layer 30 ranges from about 90 pm to about 110 pm, although thinner or thicker layers may also be formed and employed, fOOSSJ
• the roller (coater) 24 may be replaced by, or employed in addition to, other tools, such as a blade coater that may be desirable for spreading different types of powders.
• f 00645 in this example after the layer 30 comprising th polymeric particle composition 10 is formed over the fabrication bed 26, the layer 30 is exposed to heating (as shown in Fig, 38), Heating may be performed to pre-heat the polymeric particle composition 10.
• the heating temperature be belo the lowest melting temperature of the polymeric particles 12, 14, 16 in the polymeric particle composition 10,
• this temperature may be between about 2 "C below and about 100 * C below the melting temperature of the polymeric particles ⁇ e.g., between about 5 * C below and about 50 e C below, between about 10 °C below and about 30 *C below, etc. 84030581
• Pre-heating the layer 30 of the polymeric particle composition 10 may be accomplished using any suitable heat source that exposes the polymeric particle composition 10 in the fabrication bed 28 to the beat. Examples of suitable heat sources include thermal or light radiation sources.
• a liquid suspension 32 (e.g., of the aforementioned coalescent fluid), which may contain a coalescent agent and/or a plurality of nanoparticles, is selectively applied on at least a portion of the polymeric particle composition 10 in the laye 30, as shown in Fig, 3C.
• the liquid suspension 32 comprises a coalescent agent , such as any of those described herein, and nanoparticles, suefi as any of those described herein.
• An example of suitable liquid suspension 32 includes an aqueous dispersion containing at least one coalescent agent and nanoparticles.
• the coalescent agent may comprise a radiation absorbing binding agent and may be present at any of the amount described herein.
• examples of the coalescent agent include an infrared light absorber, a near infrared light absorber, or a visible light absorber.
• the coalescent agent may be an ink-type
• formulation including carbon black such as, for example, the ink formulation commercially known as C 997A available from Hewlett-Packard Company.
• inks Including visible light enhancers are dye-based colored ink and pigment-based colored ink.
• the coalescent agent may be present at between about 1 wt% and about 4 wt%, relatively to the polymeric powders.
• the liquid suspension: 32 is dispensed from an inkjet distributor 34.
• the distributor 34 may be any suitable printhead, such as a thermal Inkje printhead or a piezoelectric Inkjet printhead.
• the distributor 34 may comprise at least one printhead. While a single printhead is shown in Fig, 3C S multiple prirtthea s may be used that span the width of the fabrication had 26.
• the distributor 34 may be attached to a moving XY stage (not shown) that moves the distributor 34 adjacent to the fabrication bed 28 in order to dispose the liquid suspension 32 in desirable area s) 38,
• the distributor 34 may be programmed to receive commands from; the central processing unit, particularly the controller thereof, and to dispose the liquid suspension 32 according to a pattern for the first layer of the 3D object.
• the distributor 34 may selectively apply the liquid suspension 32 on those portions of the layer 30 that are to be fused to become the first layer of the 3D object.
• the liquid suspension 32 will be deposited in a square patem o a circular pattern (from a top view), respectively, on at least a portion of the layer 30 of the polymeric particle composition 10.
• the liquid suspension 32 is disposed, for example, in a square pattern over the area 38 of the layer 30 and not on the areas 38,
• the aqueous nature of the liquid suspension 32 may enable the liquid suspension 32 to infiltrate, at least partially, into the polymeric powder particle composition layer 30.
• the liquid suspension 32 infiltrates into the cavities between the polymeric particles. While the liquid suspension 32 is described as aqueous in this example, nonaqueous suspensions may also be employed,
• the liquid suspension 32 is selectively applied in the desired area(s) 38 , the entire layer 30 of the polymeric particle composition 10 and the liquid suspension 32 applied: to at least a portion thereof are exposed to radiation .
• the application may involve at least one of a thermal Inkjet printer and a piezoelectric Inkjet printer. This is shown in Fig. 3D. 84030581
• the energy source 40 may refer to any source that may emit an energy.
• the energy herein may comprise any suitable radiant energy; depending on the application.
• the energy may comprise at least one of infrared-light, halogen light, microwave, and laser heating.
• the radiation-energy is emitted from an energy source 40, such as an IR, near-IR, UV, or visible curing lamp, IR, riear- iR, UV, or visible light emitting diodes (LED), or lasers with specific wavelengths,
• the energy source 40 employed may depend, at least in part, on the type of liquid suspension 32, particularly the coaiescent agent, that is used-
• the energy source 40 may be attached, for example, to a carriage that also holds the disihbutorfs) 34.
• the carriage may move the energy source 40 into a position that is adjacent to the fabrication bed 26,
• the energy source 40 may be programmed to receive commands from the central processing unit and to expose the layer 30 and liquid suspension 32 to radiation.
• the length of time the radiation is applied for, or energy exposure time may be dependent, fo example, on at least one of:
• characteristics of the energy source 40 ; characteristics of the polymeri power material 10; and characteristics of the liquid suspension 32.
• Th energy source 40 may apply light, as an example of radiant energy, to the polymeric particles to cause the solidification of portions of the polymeric particles according to where coaiescent agent has been delivered or has penetrated.
• th light source is an infra-red (IR) or a near infrared Sight source, or a halogen Sight source.
• the light source may be a single light source or an array of multiple light sources.
• the light source is configured to apply light, energ in a substantially uniform manner simultaneously to the whole surface of a layer of polymeric particles.
• the light source is configured to apply energy to only certain area(s) of the whole surface of a layer of polymeric particles, in these examples, iight sourc ma be moved or scanned across the layer of polymeric particles, such that a substantially equal amount of energy is applied to the selected areas or across the whole surface of a layer of polymeric particles.
• T " tengf h of lime the radiation is applied for, or the energy exposure time, may be dependent, for example, on one or more of: characteristics of the radiation source; characteristics of the materials involved (e.g., polymeric particles and coalescent agent),
• variations in the fusing level may be achieved by after! ng (increasing or decreasing) the energy exposure time along the X, Y, and/or Z axes.
• the radiation exposure time may be the highest in the first layer and decrease in subsequently formed layers.
• variations in the level of fusing may be achieved by altering (increasing or decreasing) the amount of coalescent agent that is applied along the X s Y, and/or Z axes.
• the coalescent agent may enhance the absorption of the radiation, convert the absorbed radiation to thermal energy, and/or promote the transfer of the thermal heat to the polymeric particle composition 10 In contact therewith (i.e.. in the area 38), In one example, the coalescent agent sufficiently elevates the temperature of the polymeric particle composition 10 in the area 38 abov the melting temperaiure ⁇ s), allowing curing (e.g., sintering, binding, fusing, etc. ) of the particles 12, 14, 16 to tak place. The coalescent agent may also cause, for example, heating of the polymeric particle composition 10 below its melting temperature but to a temperature suitable to cause softening and bonding of the particles 12, 14, 18.
• area(s) 36 not having the coalescent agent applied thereto absorb less energy, and thus the polymeric particle composition 10 within these area(s) 36 generally does not exceed the melting temperature(s) of the particles 12. 14, 14, and does not cure. This causes one layer 42 of the 3D object 44 (see Fig. 3E) to be formed .
• subsequently formed layers 46, 48, 50 may have any desirable shape and/or thickness and may b the same as or different from any other layer 42, 48, 48, 50 depending upon the size, shape, etc, of " the 3D object 44 that is to be formed.
• the delivery piston 22 is pushed closer to the opening of the delivery bed 20, and the stipply of the polymeric particle composition 10 in the delivery bed 20 is diminished (compared, for example, to Fsg. 3A at the outset of the method).
• the fabrication piston 28 is pushed further away from the opening of the fabricatio bed 26 in order to accommodate the subsequent !ayerfs) of poiymeric particle composition 10 and selectively applied liquid suspension 32 containing the coalescent agent and rtanoparticies. Since at least som of the polymeric particle composition 10 remains uncured after each layer 42, 46, 48., 50 is formed in this example, the 3D object 44 is at least partially surrounded by the uncured poiymeric particle composition 10 in the fabrication bed 26.
• th 3D object 44 When th 3D object 44 is formed, it may be separated and removed from the fabrication bed, and the uncured polymeric particle composition 10 remaining in the fabrication bed 28 may be reused.
• the combination of poiymeric particles, coalescing and coalescence modifier agents, and light energy may be selected for an object slice so that (1) polymeric particles with no coalescent agent does not coalesce whe 84030581
• the system 18' includes a central processing unit 52 that controls the general operation of the additive printing system 1 S ! .
• the central processing unit 52 may comprise a controller, such as a microprocessor-based controller, that is coupled to a memory 58, for example using a communications bus (riot shown).
• the memory 58 may store the machine ⁇ e.g., computer) readable instructions 54,
• the central processing unit 62 may execute the instructions 64 and thus may control operation of the system 18' in accordance with the
• the printing system 18' Includes a coalescent agent distributor 34 to selectively deliver a coatescent fluid comprising a coalescent agent and nanoparticles ⁇ e.g., in a isquid suspension) to a layer (not shown in this figure) of polymeric particles provided on a support member 62,
• the support member 82 ha dimensions ranging from about 10 cm by about 10 cm up to about 100 cm by about 100 cm, although the support member 62 may have larger or smaller dimensions depending upon the 3D object 44 that Is to be formed.
• the central processing unit 62 may control the selective delivery of the coalescent agent and/or nanaparticies to the layer of th polymeric particles in accordance with delivery control data 64.
• the distributor 34 is a phnthead, such as a thermal printhead or a piezoelectric InkJet printhead.
• the distributor 34 ma be a drop-on-demand printhead or a continuous drop printhead.
• the distributor 34 may be used io deliver selectively the coaleseeni fluid, including a coalesceni agent and nanopariicles, when in the form of a suitable fluid, such as In a liquid suspension.
• a suitable fluid such as In a liquid suspension.
• the coalescent agent may include a liquid carrier, such as water and/or any other suitable solvent and/or dispersant, to enable si to be delivered via the distributor 34.
• the distributor 34 is selected to deliver drops of the liquid suspension containing coalescent agent and nanoparticles a a resolution ranging from about 300 dots per inch (" ⁇ ) to about 1200 DPS. In another example, the distributor 34 is selected to be able to deliver drops of the liquid suspension at a highe or lower resolution,
• T e distributor 34 may include an arra of nozzles through which the distributor 34 is able to selectively eject drops of fluid, in one example, each drop may be In the order of about 10 pico liters (pi) per drop, although It is contemplated that a higher or lower drop size may be used In some examples, distributor 34 is able to deliver variable size drops, 00373
• the distributor 34 may be an integral part of the printing system 18 ! , or they may be user replaceable. When the distributor 34 Is user replaceable, it may be removably insertable into a suitable distributor receiver or interface module (not shown).
• a single Inkjet prinihead is employed to deliver selectively different types of the coalescent agents in one or multiple liquid suspensions.
• a first set of prlnihe&d nozzles of the prinihead may be configured to deliver one type of coalescent agent and a second set of prinihead nozzles of the prinihead ma be configured to deliver another type of coalesceni agent.
• the distributor 34 has a length that enables it to span the whole width of the support member 82 in a page-wide array configuration.
• the page-wide arra configuration Is achieved through a suitable arrangement of multiple printheads.
• the page-wide array configuration Is achieved through a single printhead with an array of nozzles having a length to enable it to span the width of the support member 82. in other words
• the distributor 34 may have a shorter length that does not enable it to span the whole width of the support member 62.
• the distributor 34 may be mounted on a movable carriage to enable it to move bi-directionally across the length of the support member 82 along the illustrated y-axis. This may enable selective delivery of the liquid suspension across the whole width and length of the support member 62 in a single pass.
• the distributor 34 may be fixed while the support member 82 is configured to move relative thereto,
• the term “ idth” may refer to the shortest dimension in the plane parallel to the x and y axes shown in Fig. 4, and the term “length” to the longest dimension m this plane.
• the term “width” may be interchangeable with the term “length.”
• the distributo 34 may have a length that enable it to span th whol length of the support member 62 while the movable carriage may move bi- directionally across th width of the support membe 62.
• the distributor 34 may also be movable bi-directionally across the width of the support member 82 in the illustrated x ⁇ axis. This configuration may enable selective deliver of the liquid suspension across the whole width and length of the support membe 62 using multiple passes.
• e distributor 34 may include therein a supply of the liquid suspension ⁇ or ma be operatively connected to a separate suppl of the liquid suspension 32.
• the printing system 18 s also includes a polymeric particle composition distributor 80.
• This distributor 60 is used lo provide the layer (e.g. , layer 30) of the polymeric particle composition 10 on the support member 62
• Suitable polymeric particle composition distributors 60 may include, for example, a wiper blade and a roller.
• 009 ⁇ 3 polymeric particle composition 10 may be supplied to the polymeric particle composition distributor 80 from a hopper or other suitable delivery system, in the example shown, the polymeric particle composition distributor 60 moves across the length (y-axls) of the support, member 62 to deposit a layer of the polymeric particle composition 10, As previously described, a first layer of polymeric particle composition 10 will be deposited on the support member 62,. whereas subsequent layers ot the polymeric particle composition 10 will be deposited on a previously deposited (and solidified) layer,
• Trie support member 82 may also be movable along the z-axis.
• the support member 82 is moved in the z-direction such that as new layers of polymeric particle composition 10 are deposited, a predetermined gap is maintained between the surface of the most recently formed layer and the lower surface of the distributor 34.
• the support member 62 is fixed along the z-axis, and the distributor 34 ma be movabl along the z-axis, 00973 Similar to the system 18 as shown i Figs.
• the system 18 also includes the energy source 40 to apply energ to the deposited layer of polymeric powder material 10 and the liquid suspension 32 to cause the solidification of portlon(s) 38 of the polymeric powder material 1 .
• An of the previously described energy sources 40 may be used, in one example, the energy source 40 is a single energy source that is able to uniformly apply energy to the deposited materials, and in another example, energy source 40 includes an array of energy sources to uniformly apply energy to the deposited materials. 84030581
• the energy source 40 is configured to apply energy in a substantially uniform manner to the entire surface of fhe deposited polymeric particle composition 10.
• This type of energy source 40 may be referred to as an unfocused energy source. Exposing the entire layer to energy Simultaneously may help increase the speed at which a three-dimensional object may be generated,
• the energy source 40 may be mounted on the movable carriage or may be in a fixed position .
• central processing unit 52 may control the energy source 40.
• the amount of energy applied may be in accordance with delivery control data 84,
• the system 18' may also include a pre-heater 84 that is used to pre-rseat the deposited polymeric powder material 10 (as shown and described in reference to Fig. 38).
• the use of the pre-heater 64 may help reduce the amount of energy that has to be applied by the energy source 40.
• a pulverulent layer comprising polymeric particles is formed over a substrate.
• the layer may be formed over a substrate.
• a regular roller cosier and/or a blade coater may be employed for the formation.
• the pulverulent layer may comprise any of the polymeric particles as described above and cavities between the particles.
• the polymeric particles may have any of the aforedescribed sizes.
• the particles comprise a polyamide, such as PA-12.
• tbe particles have an average size of between about 5 pm and about 250 pm ⁇ e.g., between about: 10 pm: and about 150 pm.
• mono- dispersed polymeric particles of a pre-designated size are employed .
• a liquid suspension comprising a coalescent agent, as any of those described above, and nanoparticies, as any of those described above, is disposed over at least a portion of the pulverulent layer.
• the disposition may involve Inkjet printing.
• the Inkjet printing may involve at least one of a thermal printer and a piezoelectric printer, as described above.
• the liquid suspension may infiltrate into the cavities of the layer.
• the infiltrating liquid suspension, particularly the nanoparticies therein, may fill the cavities in the layer.
• the coalescent agent may infiltrate the layer and be in close proximity to both the polymeric partscles and the nanoparticies.
• the coalescent may comprise any suitable material, such as any of those described herein.
• the coalescent agent comprises at least one of a carbon black and an NIR dye at between about 1 wt% and about 4 wt%.
• the nanoparticies ma comprise the same or different material as/from the polymeric particles.
• the nanoparticies ma be spherical nanoparticies.
• the nanoparticies may be present at any suitable loading value in the liquid suspension (of the coalescent fluid), such as any of the amount described herein.
• the nanoparticies and the polymeric particles both comprise a
• thermoplastic in this example, the thermoplastic is PA-12, in this example, to form a dense PA-12 layer, 50 pm PA-12 particles are employed to form the base layer (step 1), followed by jetting a liquid suspension comprising a coalescent agent, as any of those described above (e,giller comprises at least one of a carbon black and an NIR dye at between about 1 t% and about 4 wt%) and PA-12 nanoparticies (about 50-500 nm, about 10-40 wt% loading with respect to the liquid suspension) onto the base layer.
• a different material composition constitutes the nanoparticies which serve to modulate the final properties of the 3D parts.
• 50 pm PA-12 particles are employed to form the base layer (step 1 ), followed by 84030581
• a coaiesoent agent as any of those described above (e.g. , comprises al least one of a carbon black and an NIR dye ai between about 1 wt% and about 4 wt;%) and nano artscles comprising a glass (e.g., silica) (about 50-500 nm, about 10-40 wt% loading with respect to the liquid suspension).
• the object slice and/or also the final resultant 3D object may have a high compaction level, such as a! least 0.5 - e.g., greater than about 0,8, about 0.7, about 0.8, about 0.9, about 0.95, about 0.99, or higher.
• the compaction level may refer to volumetric % of the particles in a material; o in corollary, the lack of voids caviies present in a material. Other values are also possible,
• Step 3 The laye is exposed to a radiation energy such that an object slice (of the final 3D object) is formed.
• the radiation may be, for example,
• Fig. 8 illustrates one example of the cross-sectional view of an object slice described herein. As shown Fig. 6, the schematic, the object slice 42 comprises
• White Fig. 8 shows that the nanoparticles have different sizes
• nanoparticles 71 may have the same size. Also, Fig. 8 shows that the micrometer- 84030581
• Step 5 are repetition of steps 1 and 2.
• steps 1 , 2, and 3 may be repeated until a 3D object is formed.
• Step 6 The final resultant 3D object is separated from the substrate. Any suitable technique of separating may be employed.
• a thin layer of nylon powder is spread and heated to close to 150 °C, Then it was printed with a liquid suspension containing carbon black as the coaleseent agent where the part has to be formed. It was exposed to a light source wherein carbon black absorbs energy and converts it to thermal energy. As a result, the powder reaches to its melting temperature and fuses to form the cross section. More layers are fabricated until the desired final 3D object is formed. In some instances, at least one modifier agent is added to mitigate thermal bleed so as to improve the surface quality.
• the process may comprise disposing a modifier agent to at least one of the object slice and the 3D object to mitigate thermal bleed.
• the modifier agent may be any of those aforedescribed.
• the modifier agent may be applied to, fo example, around the perimeter of the cross section of at least one of one of the object slice and the 3D object.
• the process method may further comprise separating the 3D object from the substrate. The separation may be carried out at any temperature.
• the 3D object may be removed from the substrate whe the temperature of the 3D subject is lower than about 200 °C - e.g. s lower than about 180 C C, or lower. Depending on the application, particularly the materials Involved, other temperatures are also possible.
• the method may further comprise removing from the object slice (or the final 3D object) particles that are not fused. The removal may be accomplished by any suitable process. For example, the removal 84030581
• the method may involve by at least one of brushing, water-jet cleaning, sonic cleaning, and blasting.
• Resultant 3D Object 0112J The methods and systems described herein may be employed to obtain dense polymeric powder layer while not affecting the infiltration of a coalescent agent. In one example, the methods described herein achieve in-situ layer densification having the densification ratio as described heroin.
• ''densification ratio * may refer to the levei of compaction (e.g., density) achieved divided by the target compaction level (e.g., density).
• the high densification ratio facilitates ensuring good fusing of the particles within the layer and/or between multiple layers.
• constituents of a powder layer are separated info at least two portions: (i) poiymeric particles and (si) nanoparticles that may or may not comprise a polymer.
• the polymeric particles may be mono-dispersed particles.
• the nanoparticles are present in the coalescent agent containing liquid suspension.
• the aforementioned at least two separate constituents are combined to facilitate layer compaction and in-situ densification. Not to he bound by any particular theory , but capillary action may ensur good sedimentation and packing of the nanoparticies among the cavities within a layer and/or uniform distribution of th coalescent agent.
• the methods described herein may mitigate, minimize, or even prevent, volumetric shrinkage and surface roughness of the final 3D parts. Additionally, by selecting the appropriate combination of the
• nanoparticies and the base poiymeric particles allow tailoring the mechanical property of the final 3D object.
• the high density of the layer may be reflected in the low porosity thereof.
• the densification ratio of the layer may be at least about 0.6 ⁇ e.g., at least about 0.7, about 0,8, about 0.9, about 0.95, about 0.99, or higher.
• the porosity of the layer is lower than about 50 (volume) % ⁇ e.g . t lower than about 84030581
• the 3D object may have the same or different density value as/from the layer.
• the object slice and/or 3D object are at least substantially free of cavities.
• the object slice has a denslficaion ratio of at Seas! about 0.80 - e.g., at least about 0,86, about 0,90, about 0,95, about 0.99, or higher.
• the software code may be executed on an suitable processor or collection of processors, whether provided in a single computer or distributed among multiple computers.
• Various examples described herein may be embodied at least in part as a non-transitor machine-readable storage medium (or multiple machine-readable storage media) - e.g., a computer memory, a floppy disc, compact disc, optical disc, magnetic tape, flash memory; circuit configuration in Field Programmable Gate Arrays o another semiconductor device, or another tangible computer storage medium or non-transitory medium) encoded with at least one machine- readable instructions thai when executed on at least one machine (e.g., a computer or another type of processor), cause at least one machine to perform methods that implement the various examples of the technology discussed herein.
• the computer readable medium or media may be transportable, such that the program or programs stored thereon may be loaded onto at least one computer or other processor to implement the various examples described herei .
• machine-readable instruction are employed herein in a generic sense to refer to any type of machine code or set of machine-executable
• the machine-readable instructions may include, but not limited to, a software or a program.
• the machine may refer to a computer or another type of processor. Additionally, when executed to perform the methods described herein:, the machine-readable instructions need not reside on a single machine, but may be distributed in a modular fashion amongst a number of different machines to implement the various examples described herein.
• Machine-executable instructions may be in many forms, such as program modules, executed by at least one machine (e.g., a computer or another type of processor).
• program modules include routines, programs, objects, 84030581
• the technolog described herein may be embodied as a method, of which at least one example has been provided.
• the acts performed as part of the method may be ordered in any suitable way. Accordingly, examples may be constructed in which acts are performed in an order different than illustrated, which may include performing some acts simultaneously, even though shown as sequential acts in illustrative examples.
• a reference to * A and/or B when used in conjunction with open-ended language such as “comprising” may refer, in one example, to A only (optionally including elements other than B); in another example, to B only (optionally including elements other than A); in yet another example, t both A and 8 (optionally including other elements); etc.
• the phrase "at least one,” in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of tie elements In the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the Sist of elements.
• This definition also allows that elements may optionally be present other than the elements specificall identified withi the list of element to which the phrase "at least one ' refers, whether related or unrelated to those elements specifically identified.
• At least one of A and 8 * may refer, in one example, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another example, to at least one, optionaSi including more than one, 8, with no A present (and optionaSiy including elements other than A); in yet another example, to at least one, optionaSiy including mor than one, A, and at Ieast one, optionally including more than one, 8 (and optionally including other elements); etc.

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• 2014
  • 2014-09-30 US US15/510,122 patent/US10392521B2/en active Active
  • 2014-09-30 EP EP14903082.7A patent/EP3200980B1/de active Active
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